CN107267891A - Cobalt-based amorphous alloy catalytic electrode and production method thereof - Google Patents
Cobalt-based amorphous alloy catalytic electrode and production method thereof Download PDFInfo
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- CN107267891A CN107267891A CN201710462814.0A CN201710462814A CN107267891A CN 107267891 A CN107267891 A CN 107267891A CN 201710462814 A CN201710462814 A CN 201710462814A CN 107267891 A CN107267891 A CN 107267891A
- Authority
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- China
- Prior art keywords
- amorphous alloy
- catalysis electrode
- cobalt
- ball milling
- cobalt base
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Links
- 229910000808 amorphous metal alloy Inorganic materials 0.000 title claims abstract description 50
- 239000010941 cobalt Substances 0.000 title claims abstract description 29
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 29
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 230000003197 catalytic effect Effects 0.000 title abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000004080 punching Methods 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 4
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 4
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 3
- 239000000956 alloy Substances 0.000 claims abstract description 3
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 46
- 238000000498 ball milling Methods 0.000 claims description 21
- 239000011248 coating agent Substances 0.000 claims description 17
- 238000000576 coating method Methods 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 10
- 238000005452 bending Methods 0.000 claims description 9
- 238000005516 engineering process Methods 0.000 claims description 9
- 238000005253 cladding Methods 0.000 claims description 8
- 238000005476 soldering Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 238000007747 plating Methods 0.000 claims description 6
- 238000005275 alloying Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- 239000008139 complexing agent Substances 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 238000004070 electrodeposition Methods 0.000 claims description 2
- 238000004448 titration Methods 0.000 claims description 2
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 description 8
- 239000005300 metallic glass Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- IGOJDKCIHXGPTI-UHFFFAOYSA-N [P].[Co].[Ni] Chemical compound [P].[Co].[Ni] IGOJDKCIHXGPTI-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 229910001369 Brass Inorganic materials 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000010951 brass Substances 0.000 description 4
- 238000007493 shaping process Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 238000005538 encapsulation Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 3
- 229940081974 saccharin Drugs 0.000 description 3
- 235000019204 saccharin Nutrition 0.000 description 3
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- -1 neopelex Chemical compound 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- HIRWGWMTAVZIPF-UHFFFAOYSA-N nickel;sulfuric acid Chemical compound [Ni].OS(O)(=O)=O HIRWGWMTAVZIPF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/04—Amorphous alloys with nickel or cobalt as the major constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/061—Metal or alloy
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Metallurgy (AREA)
- Electrochemistry (AREA)
- Mechanical Engineering (AREA)
- Catalysts (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
A cobalt-based amorphous alloy catalytic electrode is characterized in that the electrode consists of a groove-shaped electrode frame and a pluggable catalytic electrode plate, the pluggable catalytic electrode plate is made of metal mesh coated cobalt-based amorphous alloy flaky particles, the specific component of the cobalt-based amorphous alloy flaky particles is Fe35-95 wt%, and the rest alloy elements are elements capable of being electrodeposited together with iron, such as one or the combination of more of P, Fe, Ni, Cr, Mo, W, Re and the like; the groove-shaped electrode frame is formed by punching a metal thin plate, rectangular holes are uniformly formed in two side plates of the groove-shaped electrode frame, and metal at the positions of the rectangular holes is punched and bent to form a fixed plate of the catalytic electrode.
Description
Technical field
The present invention relates to the catalysis electrode of electrochemical field, a kind of cobalt base amorphous alloy composite catalyzing electricity is related specifically to
Pole and production method.
Background technology
Non-crystaline amorphous metal is due to having the characteristics that；1. various compositions can be made in amorphous alloy in a wide range
Sample, so as to their electronic property of modulation in compared with broad range；2. catalytic active center can be in single form
It is evenly distributed in the environment of chemical homogeneous；3. amorphous alloy surface has the higher unsaturated center of concentration, and unsaturated
The ligancy at center has certain scope, thus its catalytic activity and selectivity is generally to be preferred over corresponding crystalline-state catalyst；
4. the imporosity on its surface is the problem of its surface that extends influence for having broken away from the reaction species that multinomial catalyst is present is reacted.
The reactions such as amorphous alloy catalyst can be used for being hydrogenated with, aoxidize, crack, isomerization.At present, amorphous alloy is urged
The preparation method of agent has a variety of, in general can be classified as two major classes：Liquid is quenched method and atom（Ion）Sedimentation.
Non-crystaline amorphous metal catalysis electrode is based on the two-dimentional catalysis electrode of deposition film or coating, but its reactor areas is smaller, causes production
Rate is smaller.
The content of the invention
For problem above, the present invention proposes a kind of cobalt base amorphous alloy catalysis electrode and production method.The skill of the present invention
Art solution is to provide a kind of cobalt base amorphous alloy catalysis electrode, it is characterised in that electrode is by groove profile arc-spark stand and can pull and push
Formula catalysis electrode plate constitute, can draw and insert-type catalysis electrode plate by wire netting coat cobalt base amorphous alloy sheet-like particle be made, cobalt
The specific composition of base noncrystal alloy sheet-like particle be Co35-95 wt %, remaining alloying element for can together with cobalt electro-deposition member
The combination of one or more elements in element, such as P, Fe, Ni, Cr, Mo, W, Re.Groove profile arc-spark stand is then by sheet metal punching press
Shaping, slot is uniformly offered in the biside plate of groove profile arc-spark stand, is made up of the metal punching of slot position, bending
Catalysis electrode fixed plate.
The technical solution of the present invention is to provide a kind of preparation method of cobalt base amorphous alloy catalysis electrode again, including with
Lower step：
（1）Can draw and insert-type catalysis electrode plate preparation technology
1）The production of cobalt base amorphous alloy coating
（a）Metal substrate is plated the degreasing on surface and oxide-film is removed, and metal substrate material should suitably carry out the plasticity under normal temperature
Processing；
（b）Electroplate liquid is constituted；Cobaltous sulfate 0.5-4mol/L, sour 0.2-1mol/L, complexing agent 0.5-5g/L, alloying element additive
0.2-4mol/L, water surplus；
In alloying element additive described above, iron is with soluble ferrite（Reducing agent with 0.5-2g/L）, nickel is with solubility
Nickel salt, chromium with chromic anhydride, molybdenum with sodium molybdate, tungsten with sodium tungstate, phosphorus with phosphorous acid or soluble hypophosphites, Re with Re soluble salts
Form is added；
Above-mentioned acid includes the polynary middle strong acid such as boric acid, phosphoric acid；
Above-mentioned complexing agent includes the organic complexing agents such as saccharin, neopelex, tartaric acid, citrate；
（c）Cobalt base amorphous alloy coating is prepared using plating or Brush Plating, anode uses graphite or stainless steel, and electrolyte temperature is
40-90 DEG C, titration strong acid solution makes Ph values be not more than 1；
2）The stripping of amorphous alloy coating
Using method mechanically or physically, such as stretching, bending, rolling reductions, scraping method make amorphous alloy coating and metal
Substrate is peeling-off；
3）Particle it is broken
（a）Using ball mill, planetary ball mill etc., the amorphous particle of peeling is subjected to ball under the conditions of vacuum or gas shield
Mill, using ball milling（3-10min）, stalling（3-10min）The mode of this interval circulation, or additional can be forced simultaneously using ball milling
The mode ball milling of cooling, ball milling total time（Time comprising ball milling and stalling）For 0.5-3h, ratio of grinding media to material is 2-8:1；
（b）It is sieved into the cobalt base amorphous alloy particle of different thicknesses；
4）Can draw and insert-type catalysis electrode metallic cover net shaping
Using wire netting, cut, bend, soldering prepares tabular cladding wire netting,
5）The injection and encapsulation of Amorphous Alloy Grain
Cobalt base amorphous alloy particle is injected into tabular cladding wire netting, tabular cladding metal is then closed using modes such as solderings
Net.
（2）The preparation technology of groove profile arc-spark stand
Using copper or copper alloy thin plate, cutting, punching, bending prepare groove profile arc-spark stand.
（3）It is assembled into cobalt base amorphous alloy catalysis electrode
Can draw and insert-type catalysis electrode plate be placed in two catalysis electrode fixed plates, cobalt base amorphous alloy catalysis electrode is made.
Compared with prior art, advantages of the present invention：
1. due to using cobalt base amorphous alloy particle, as catalyst, the catalytic performance of electrode can be improved；
2. due to preparing cobalt base amorphous alloy particulate using plating+stripping+broken, particulate basic configuration is lamellar, this raising
The surface area of amorphous alloy catalyst reaction；
3. due to using groove profile arc-spark stand, and offering slot in biside plate, end is also unclosed, improves to greatest extent
Solution increases the relative flow of catalysis electrode and solution in the flowable of electrode interior, can improve the catalysis effect of catalysis electrode
Rate；
4. due to using draw and insert-type structure, therefore the reactor areas of electrode and the spacing of catalysis electrode plate are easy to adjustment,
Also allow for changing and maintenance.
Brief description of the drawings
Fig. 1 is present device schematic diagram.Wherein, groove profile arc-spark stand（1）, can be made of copper or copper alloy thin plate；Can
Draw and insert-type catalysis electrode plate（2）, it is made of plate-shape metal net cladding cobalt base amorphous alloy particle；Catalysis electrode fixed plate（3）；
Slot（4）.
Embodiment
The invention will be further described with reference to embodiments.
1. the production of cobalt-nickel non-crystaline amorphous metal catalysis electrode
（1）Can draw and insert-type catalysis electrode plate preparation technology
1）The production of cobalt nickel amorphous alloy coating
（a）Metal substrate uses brass sheet, and the degreasing of brass surface and oxide-film are removed；
（b）Electroplate liquid is constituted；The mol/L of cobaltous sulfate 2.5, the mol/L of phosphoric acid 0.55, the g/L of saccharin 0.8, sodium citrate 0.3g/L,
Nickel sulfate 0.7mol/L, nickel chloride 0.5mol/L, water surplus；
（c）Cobalt nickel amorphous alloy coating is prepared using galvanoplastic, anode uses graphite, and electrolyte temperature is 75 DEG C, titrated sulfuric acid
Solution makes Ph values be 1；
2）The stripping of amorphous alloy coating
Make cobalt nickel amorphous alloy coating and brass sheet peeling-off using the method for alternating bending；
3）Particle it is broken
（a）Using planetary ball mill, by the way of this interval circulation of the min of ball milling 5,5 min of stalling, by the non-of peeling
Brilliant particle carries out ball milling, ball milling total time under vacuum（Time comprising ball milling and stalling）For 1 h, ratio of grinding media to material is 3:1；
（b）It is sieved into the cobalt nickel Amorphous Alloy Grain of different thicknesses；
4）Can draw and insert-type catalysis electrode metallic cover net shaping
Using the stainless steel mesh of 100 mesh, cut, bend, soldering prepares tabular cladding wire netting,
5）The injection and encapsulation of Amorphous Alloy Grain
Injection in wire netting is coated toward tabular, more than the cobalt nickel Amorphous Alloy Grain of 100 mesh, then to close using modes such as solderings
Wire netting is coated into tabular.
（2）The preparation technology of groove profile arc-spark stand
Cut using sheet brass, punching, bending prepare groove profile arc-spark stand.
（3）It is assembled into cobalt nickel non-crystaline amorphous metal catalysis electrode
Can draw and insert-type catalysis electrode plate be placed in two catalysis electrode fixed plates, cobalt nickel non-crystaline amorphous metal catalysis electrode is made.
2. cobalt-nickel-phosphor non-crystaline amorphous metal catalysis electrode
（1）Can draw and insert-type catalysis electrode plate preparation technology
1）The production of cobalt-nickel-phosphor amorphous alloy coating
（a）The degreasing of 08F surface of thin steel sheet and oxide-film are removed；
（b）Electroplate liquid is constituted；Cobaltous sulfate 3.5mol/L, the mol/L of boric acid 0.7, saccharin 0.8g/L, the g/L of tartaric acid 0.5, sulfuric acid
Nickel 1.5mol/L, sodium hypophosphite 0.75mol/L, water surplus；
（c）Cobalt-nickel-phosphor amorphous alloy coating is prepared using Brush Plating, anode uses graphite cake, and electrolyte temperature is 70 DEG C, drop
Determining strong acid solution makes Ph values be 1, and the relative moving speed of battery lead plate is 80 mm/s, and the average current density of battery lead plate is 15A/
cm2；
2）The stripping of amorphous alloy coating
Make amorphous alloy coating and 08F sheet metals peeling-off using the method for biaxial tension；
3）Particle it is broken
（a）Using planetary ball mill, by the way of this interval circulation of ball milling 3min, stalling 5min, by the amorphous of peeling
Ball milling, ball milling total time are carried out under particle nitrogen protective condition（Time comprising ball milling and stalling）For 0.5 h, ratio of grinding media to material is 5:
1；
（b）It is sieved into cobalt-nickel-phosphor Amorphous Alloy Grain of different thicknesses；
4）Can draw and insert-type catalysis electrode metallic cover net shaping
Using the wire netting of 100 mesh, cut, bend, soldering prepares tabular cladding wire netting,
5）The injection and encapsulation of Amorphous Alloy Grain
Cobalt-nickel-phosphor Amorphous Alloy Grain that injection in wire netting is more than 100 mesh is coated toward tabular, then using modes such as solderings
Close tabular cladding wire netting.
（2）The preparation technology of groove profile arc-spark stand
Using bronze thin plate, cutting, punching, bending prepare groove profile arc-spark stand.
（3）It is assembled into cobalt-nickel-phosphor non-crystaline amorphous metal catalysis electrode
Can draw and insert-type catalysis electrode plate be placed in two catalysis electrode fixed plates, cobalt-nickel-phosphor non-crystaline amorphous metal catalysis electrode is made.
Claims (5)
1. a kind of cobalt base amorphous alloy catalysis electrode, it is characterised in that electrode is by groove profile arc-spark stand and can draw and insert-type catalysis electrode
Plate constitute, can draw and insert-type catalysis electrode plate by wire netting coat cobalt base amorphous alloy sheet-like particle be made, cobalt base amorphous alloy
The specific composition of sheet-like particle be Fe35-95 wt %, remaining alloying element for can together with iron electro-deposition element, such as P, Fe,
The combination of one or more elements in Ni, Cr, Mo, W, Re etc.；Groove profile arc-spark stand is then by sheet metal punch forming, in groove profile
The biside plate of arc-spark stand uniformly offers slot, and catalysis electrode is made by the metal punching of slot position, bending
Fixed plate.
2. the production method of cobalt base amorphous alloy catalysis electrode, it is characterised in that comprise the following steps：（1）Can draw and insert-type catalysis
The preparation technology of battery lead plate；（2）Using copper or copper alloy thin plate, cutting, punching, bending prepare groove profile arc-spark stand；（3）Can take out
Insert formula catalysis electrode plate to be placed in two catalysis electrode fixed plates, cobalt base amorphous alloy catalysis electrode is made.
3. as claimed in claim 2, can draw and insert-type catalysis electrode preparation technology, it is characterised in that production stage is：1）Cobalt-based
The production of amorphous alloy coating；2）Make amorphous alloy coating peeling-off with metal substrate using method mechanically or physically；3）
The amorphous particle of peeling is subjected to ball milling under the conditions of vacuum or gas shield；4）Using wire netting, cutting, bending, soldering system
Slave board shape coats wire netting；5）Cobalt base amorphous alloy particle is injected into tabular cladding wire netting, is closed using modes such as solderings
Tabular coats wire netting.
4. as claimed in claim 3, the production of co-based alloy coating, it is characterised in that：Electroplate liquid is constituted；Cobaltous sulfate 0.5-
4mol/L, polynary middle strong acid 0.2-1mol/L, complexing agent 0.5-5g/L, alloying element additive 0.2-4mol/L, water surplus；Adopt
Cobalt base amorphous alloy coating is prepared with plating or Brush Plating mode, anode uses graphite or stainless steel, and electrolyte temperature is 40-90
DEG C, titration strong acid solution makes Ph values be not more than 1.
5. as claimed in claim 3, amorphous particle ball milling under the conditions of vacuum or gas shield, it is characterised in that：Ball milling method
Using ball milling（3-10min）, stalling（3-10min）The mode of this interval circulation, or additional can force cold simultaneously using ball milling
But mode ball milling, ball milling total time（Time comprising ball milling and stalling）For 0.5-3h, ratio of grinding media to material is 2-8:1.
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